WO2011029507A1 - Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation - Google Patents
Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation Download PDFInfo
- Publication number
- WO2011029507A1 WO2011029507A1 PCT/EP2010/004942 EP2010004942W WO2011029507A1 WO 2011029507 A1 WO2011029507 A1 WO 2011029507A1 EP 2010004942 W EP2010004942 W EP 2010004942W WO 2011029507 A1 WO2011029507 A1 WO 2011029507A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolyte
- copper layer
- plating
- copper
- zinc
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Definitions
- the invention relates to a process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation.
- the deposition of copper on zinc articles or zinc diecastings is adequately known to those skilled in the art (ref 4).
- the first step in the copper plating of zinc diecastings is, according to the prior art (refs 1, 2, 3), the deposition of copper from an alkaline cyanide electrolyte. Subsequently, a bright copper layer from an acidic electrolyte or a nickel or bronze layer is usually deposited.
- a particular difficulty in the plating of zinc diecastings is the structure of the base material formed on injection moulding.
- the casting is coarsely crystalline and permeated with voids in the interior. Only a thin outer layer is dense and pore-free. The outer layer is formed during injection moulding by rapid cooling of the melt on the walls of the casting mould. Only this outer casting skin can be electroplated according to the prior art. However, the casting skin is very sensitive and is sometimes chemically attacked and damaged during the pretreatment by degreasing and pickling, so that the pores of the base material are sometimes exposed. The plating baths themselves can also damage the casting skin. A firmly adhering coating can no longer be applied to the damaged surface.
- blister formation frequently occurs as a result of the pretreatment baths or the electrolyte penetrating through the damaged casting skin into the pores of the base material.
- the liquid which has penetrated in vaporizes and pushes the applied coating outward to form blisters or raised regions.
- the copper layer flakes off.
- This object is achieved by a process which comprises the following process steps: a) deposition of a first copper layer having a thickness of less than 1 ⁇ from a
- a thin copper layer having a thickness of less than 1 ⁇ is firstly deposited from a pyrophosphate-containing copper electrolyte on the casting skin of the zinc diecastings.
- the casting skin is generally damaged.
- the electrolyte can penetrate into the now open porous microstructure of the zinc diecasting during the pretreatment or during plating. It is therefore of great importance to the process that the copper layer applied in the first plating step still has sufficient porosity for the carrier liquid of the electrolyte which has vaporized during the subsequent heat treatment to be able to escape.
- This layer should therefore be no thicker than 1 ⁇ and preferably has a thickness in the range from 0.1 to 0.5 ⁇ , in particular from 0.2 to 0.3 ⁇ .
- the parts are rinsed and dried by storage at a temperature of from 100 to 180°C, preferably from 120°C to 160°C and particularly preferably about 140°C, for a sufficient time, e.g. from 10 to 60 minutes.
- a sufficient time e.g. from 10 to 60 minutes.
- the copper layer present as a result of the first plating step is, because of its low thickness, still porous and not impermeable to the vapour being formed, so that the vapour formed on heating can escape. Only the solid constituents (salts) of the electrolyte remain in the pores and these do not interfere further. The presence of residual electrolyte salts can be confirmed, for example, by means of SEM and/or EDX studies. Rinsing is preferably carried out using water and is adequately known to those skilled in the art.
- plating is continued, if appropriate in the same pyrophosphate-containing electrolyte, until from about 5 to 50 ⁇ , preferably from 10 to 30 ⁇ , particularly preferably from 10 to 20 ⁇ , of copper have been deposited.
- the thin copper layer which is already present, at the beginning of the second plating step obviously prevents penetration of liquid electrolyte into the porous zinc base material.
- the parts which have been plated in this way withstand storage at 150°C for about 30 minutes without blister formation or even flaking.
- the copper layer in the first substep a) can be deposited by means of an electrochemical process. Electrolytic deposition (ref 4) is possible here.
- the second copper coating can be deposited reductively or preferably by means of an electrolytic process.
- electrolytic processes essentially 3 different plating processes may be mentioned: 1. Drum plating for bulk material and mass-produced parts:
- medium working current densities are employed (order of magnitude: 0.2 - 5 A/dm 2 )
- the first two plating processes tend to be of importance for plating with copper, with either drum plating (low current densities) or rack plating (medium current densities) being possible depending on different electrolyte types.
- the application of the copper layer to the zinc diecasting in both process steps a) and c) is, as mentioned above, advantageously carried out by means of an electrolytic process.
- the metal to be deposited is constantly kept in solution during the process, regardless of whether electroplating is carried out in a continuous process or a discontinuous process.
- the electrolyte according to the invention contains pyrophosphate as complexing agent.
- the amount of pyrophosphate ions present in the electrolyte can be set in a targeted manner by a person skilled in the art. It is limited by the fact that the concentration in the electrolyte should be above a minimum amount in order to be able to bring about the abovementioned effect to a sufficient extent.
- the amount of pyrophosphate to be used is guided by economic considerations. In this context, reference may be made to EP1146148 and the relevant information given therein.
- the amount of pyrophosphate to be used in the electrolyte is preferably 50 - 400 g/1.
- the pyrophosphate can, if it is not introduced as salt constituent of the metals to be deposited, be used as alkali metal diphosphate or alkaline earth metal diphosphate or as H 2 P 2 0 7 in combination with an alkali metal or alkaline earth metal carbonate/hydrogencarbonate. Preference is given to using K 2 P 2 0 7 for this purpose.
- the copper to be deposited is present in solution in the form of its ions. They are preferably introduced in the form of water-soluble salts which are preferably selected from the group consisting of pyrophosphates, carbonates, hydroxycarbonates, hydrogencarbonates, sulphites, sulphates, phosphates, nitrites, nitrates, halides, hydroxides, oxide-hydroxides, oxides and combinations thereof. Very particular preference is given to the embodiment in which the copper is used in the form of the salts with ions selected from the group consisting of pyrophosphate, carbonate, hydroxycarbonate, oxide-hydroxide, hydroxide and hydrogencarbonate. What salts are introduced in what amount into the electrolyte can be decisive for the colour of the resulting layers and can be set according to customer requirements.
- concentration of copper can be set in the range from 5 to 100 g/1 of electrolyte, preferably from 10 to 50 g/1 of electrolyte.
- the resulting ion concentration is
- electrolyte particularly preferably in the range from 15 to 30 g/1 of electrolyte.
- About 15-20 gram of copper per litre of electrolyte are very particularly preferably used, with the copper being introduced as pyrophosphate, carbonate or hydroxycarbonate salt into the electrolyte.
- the pH of the electrolytes is in the range from 6 to 13 required for electroplating.
- a pH of about 7.9 - 8.1 is most preferably employed.
- the electrolytes can contain further organic additives which perform functions as brighteners, wetting agents or stabilizers.
- the electrolyte according to the invention can also dispense with the use of cationic surfactants.
- the addition of further brighteners and wetting agents is preferred only when the appearance of the layers to be deposited has to meet specific requirements.
- the addition of one or compounds selected from the group consisting of monocarboxylic and dicarboxylic acids, alkanesulphonic acids, betaines and aromatic nitro compounds is preferred. These compounds act as electrolyte bath stabilizers. Particular preference is given to using carboxylic acids,
- alkanesulphonic acids in particular methanesulphonic acid, or nitrobenzotriazoles or mixtures thereof.
- Suitable alkanesulphonic acids are mentioned in EP1001054.
- Possible carboxylic acids are, for example, citric acid, oxalic acid, gluconic acids, etc. (Jordan, Manfred, Die galvanische Abscheidung von Zinn und Zinnlegtechniken, Saulgau 1993, page 156).
- Betaines to be used are preferably those from WO2004/005528 or from Jordan, Manfred (Die galvanische Abscheidung von Zinn und Zinnlegmaschineen, Saulgau 1993, page 156).
- Particular preference is given to those disclosed in EP636713. In this context, very particular preference is given to using l-(3-sulphopropyl)pyridinium- betaine or l-(3-sulphopropyl)-2-vinylpyridiniumbetaine.
- the electrolyte according to the invention is characterized in that it is free of hazardous substances classified as toxic (T) or very toxic (T + ). It contains no cyanides, no thiourea derivatives and no thiol derivatives.
- the deposition of the copper layers can be operated at a temperature chosen on the basis of the general knowledge of a person skilled in the art. Preference is given to a range from 20 to 60°C within which the electrolytic bath is maintained during the electrolysis. More preference is given to a range of 30 - 50°C. The deposition is most preferably carried out at a temperature of about 40°.
- the deposition of the copper in steps a) and c) can be carried out in electrochemical cells which are well known to those skilled in the art (ref 1).
- electrochemical cells which are well known to those skilled in the art (ref 1).
- various anodes can be employed. It is possible to use soluble or insoluble anodes or a combination of soluble and insoluble anodes.
- soluble anodes preference is given to using anodes composed of a material selected from the group consisting of electrolytic copper, phosphorus-containing copper and copper alloys.
- insoluble anodes preference is given to using anodes composed of a material selected from the group consisting of platinated titanium, graphite, iridium- transition metal mixed oxide and special carbon material ("Diamond-Like Carbon" or DLC) or combinations of these anodes.
- DLC Diamond-Like Carbon
- mixed oxide anodes composed of iridium-ruthenium mixed oxide, iridium-ruthenium-titanium mixed oxide or iridium-tantalum mixed oxide.
- insoluble anodes may be found in Cobley, A.J. et al. (The use of insoluble Anodes in Acid Sulphate Copper
- insoluble anodes are employed, a particularly preferred embodiment of the process is obtained when the substrates to be provided with the copper layer, which represent the cathode, are separated from the insoluble anode by an ion-exchange membrane in such a way that a cathode space and an anode space are formed. In such a case, only the cathode space is filled with the nontoxic electrolyte.
- An aqueous solution containing only an electrolyte salt e.g. potassium pyrophosphate, potassium carbonate, potassium hydroxide, potassium hydrogencarbonate or a mixture thereof, is preferably present in the anode space.
- an electrolyte salt e.g. potassium pyrophosphate, potassium carbonate, potassium hydroxide, potassium hydrogencarbonate or a mixture thereof.
- ion-exchange membrane it is possible to use cationic or anionic exchange membranes. Preference is given to using membranes of Nafion having a thickness of from 50 to 200 ⁇ .
- the process of the invention and in particular the heat treatment between the two plating steps thus enables the carrier liquid of the electrolyte used to be removed to such an extent that it does not lead to blister formation or flaking during later heating of the parts.
- the copper layer is applied to the zinc from a, for example, pyrophosphate-containing electrolyte without the heat treatment according to the invention of step b)
- the liquid which penetrates into the porous base material can no longer escape during later heating of the coated parts and, due to the vapour pressure produced, leads to blister formation or flaking in the coating. This was not to be expected from the prior art.
- the plating of zinc diecastings with copper is carried out using an electrolyte solution having the following composition:
- the zinc diecastings are plated in a barrel at 40°C and a current density of 0.5 A/dm 2 for a time of 3 minutes.
- the parts are then rinsed, stored at 150°C for a time of 30 minutes and, after cooling, plated in the same electrolyte bath for a further 2 hours.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201080036696.3A CN102471911B (en) | 2009-09-11 | 2010-08-12 | Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation |
US13/395,204 US20120217166A1 (en) | 2009-09-11 | 2010-08-12 | Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation |
EP10751798A EP2475808A1 (en) | 2009-09-11 | 2010-08-12 | Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation |
JP2012528239A JP2013504685A (en) | 2009-09-11 | 2010-08-12 | Method for electro copper plating of zinc die casting with reduced tendency of blister formation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102009041250.6 | 2009-09-11 | ||
DE102009041250A DE102009041250B4 (en) | 2009-09-11 | 2009-09-11 | Process for the electrolytic copper plating of zinc die casting with reduced tendency to blister |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011029507A1 true WO2011029507A1 (en) | 2011-03-17 |
Family
ID=42983272
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2010/004942 WO2011029507A1 (en) | 2009-09-11 | 2010-08-12 | Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation |
Country Status (7)
Country | Link |
---|---|
US (1) | US20120217166A1 (en) |
EP (1) | EP2475808A1 (en) |
JP (1) | JP2013504685A (en) |
KR (1) | KR20120079065A (en) |
CN (1) | CN102471911B (en) |
DE (1) | DE102009041250B4 (en) |
WO (1) | WO2011029507A1 (en) |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3664933A (en) * | 1969-06-19 | 1972-05-23 | Udylite Corp | Process for acid copper plating of zinc |
US3716462A (en) * | 1970-10-05 | 1973-02-13 | D Jensen | Copper plating on zinc and its alloys |
US4285782A (en) * | 1980-08-06 | 1981-08-25 | The United States Of America As Represented By The United States Department Of Energy | Method for providing uranium with a protective copper coating |
EP0636713A2 (en) | 1993-07-26 | 1995-02-01 | Degussa Aktiengesellschaft | Alcaline cyanide baths for electroplating copper-tin alloys coatings |
US5558759A (en) * | 1994-07-26 | 1996-09-24 | Sargent Manufacturing Company | Metal finishing process |
EP0924320A2 (en) * | 1997-12-16 | 1999-06-23 | Totoku Electric Co., Ltd. | Method of fabricating a copper plated aluminium wire, a plated aluminium wire, an insulating plated aluminium wire, methods of fabricating thereof, and a composite lightweighted plated aluminium wire |
EP1001054A2 (en) | 1998-11-05 | 2000-05-17 | C. Uyemura & Co, Ltd | Tin-copper alloy electroplating bath and plating process therewith |
EP1146148A2 (en) | 2000-04-14 | 2001-10-17 | Nihon New Chrome Co. Ltd. | Cyanide-free pyrophosphoric acid bath for use in copper-tin alloy plating |
US6506668B1 (en) * | 2001-06-22 | 2003-01-14 | Advanced Micro Devices, Inc. | Utilization of annealing enhanced or repaired seed layer to improve copper interconnect reliability |
WO2004005528A2 (en) | 2002-07-05 | 2004-01-15 | Nihon New Chrome Co., Ltd. | Pyrophosphoric acid bath for use in copper-tin alloy plating |
US20050006245A1 (en) * | 2003-07-08 | 2005-01-13 | Applied Materials, Inc. | Multiple-step electrodeposition process for direct copper plating on barrier metals |
Family Cites Families (11)
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US2709847A (en) * | 1951-05-04 | 1955-06-07 | Bendix Aviat Corp | Cadmium plated aluminum and the method of making the same |
NL267368A (en) * | 1960-07-23 | |||
JPS4926174B1 (en) * | 1970-07-11 | 1974-07-06 | ||
US3751289A (en) * | 1971-08-20 | 1973-08-07 | M & T Chemicals Inc | Method of preparing surfaces for electroplating |
US4904354A (en) * | 1987-04-08 | 1990-02-27 | Learonal Inc. | Akaline cyanide-free Cu-Zu strike baths and electrodepositing processes for the use thereof |
CA2019568C (en) * | 1990-06-21 | 1998-11-24 | Hieu C. Truong | Coins coated with nickel, copper and nickel and process for making such coins |
JPH0499889A (en) * | 1990-08-17 | 1992-03-31 | Asahi Chem Ind Co Ltd | Production of plating film |
US7132158B2 (en) * | 2003-10-22 | 2006-11-07 | Olin Corporation | Support layer for thin copper foil |
CN1763920A (en) * | 2004-10-19 | 2006-04-26 | 中芯国际集成电路制造(上海)有限公司 | Method for extending copper seed crystal and electrochemistry coppering technique interval time |
US20080156652A1 (en) * | 2006-12-28 | 2008-07-03 | Chang Gung University | Cyanide-free pre-treating solution for electroplating copper coating layer on zinc alloy surface and a pre-treating method thereof |
CN101123127A (en) * | 2007-09-21 | 2008-02-13 | 施义明 | A micro silver plating and copper-coated copper multi-strand line and its making method |
-
2009
- 2009-09-11 DE DE102009041250A patent/DE102009041250B4/en active Active
-
2010
- 2010-08-12 WO PCT/EP2010/004942 patent/WO2011029507A1/en active Application Filing
- 2010-08-12 US US13/395,204 patent/US20120217166A1/en not_active Abandoned
- 2010-08-12 CN CN201080036696.3A patent/CN102471911B/en active Active
- 2010-08-12 EP EP10751798A patent/EP2475808A1/en not_active Withdrawn
- 2010-08-12 KR KR1020127006313A patent/KR20120079065A/en not_active Application Discontinuation
- 2010-08-12 JP JP2012528239A patent/JP2013504685A/en not_active Withdrawn
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3664933A (en) * | 1969-06-19 | 1972-05-23 | Udylite Corp | Process for acid copper plating of zinc |
US3716462A (en) * | 1970-10-05 | 1973-02-13 | D Jensen | Copper plating on zinc and its alloys |
US4285782A (en) * | 1980-08-06 | 1981-08-25 | The United States Of America As Represented By The United States Department Of Energy | Method for providing uranium with a protective copper coating |
EP0636713A2 (en) | 1993-07-26 | 1995-02-01 | Degussa Aktiengesellschaft | Alcaline cyanide baths for electroplating copper-tin alloys coatings |
US5558759A (en) * | 1994-07-26 | 1996-09-24 | Sargent Manufacturing Company | Metal finishing process |
EP0924320A2 (en) * | 1997-12-16 | 1999-06-23 | Totoku Electric Co., Ltd. | Method of fabricating a copper plated aluminium wire, a plated aluminium wire, an insulating plated aluminium wire, methods of fabricating thereof, and a composite lightweighted plated aluminium wire |
EP1001054A2 (en) | 1998-11-05 | 2000-05-17 | C. Uyemura & Co, Ltd | Tin-copper alloy electroplating bath and plating process therewith |
EP1146148A2 (en) | 2000-04-14 | 2001-10-17 | Nihon New Chrome Co. Ltd. | Cyanide-free pyrophosphoric acid bath for use in copper-tin alloy plating |
US6506668B1 (en) * | 2001-06-22 | 2003-01-14 | Advanced Micro Devices, Inc. | Utilization of annealing enhanced or repaired seed layer to improve copper interconnect reliability |
WO2004005528A2 (en) | 2002-07-05 | 2004-01-15 | Nihon New Chrome Co., Ltd. | Pyrophosphoric acid bath for use in copper-tin alloy plating |
US20050006245A1 (en) * | 2003-07-08 | 2005-01-13 | Applied Materials, Inc. | Multiple-step electrodeposition process for direct copper plating on barrier metals |
Non-Patent Citations (2)
Title |
---|
COBLEY, A.J. ET AL.: "The use of insoluble Anodes in Acid Sulphate Copper Electrodeposition Solutions", TRANS IMF, vol. 79, no. 3, 2001, pages 113114, XP001023283 |
JORDAN, MANFRED, DIE GALVANISCHE ABSCHEIDUNG VON ZINN UND ZINNLEGIERUNGEN, 1993, pages 156 |
Also Published As
Publication number | Publication date |
---|---|
DE102009041250B4 (en) | 2011-09-01 |
EP2475808A1 (en) | 2012-07-18 |
CN102471911B (en) | 2014-10-15 |
US20120217166A1 (en) | 2012-08-30 |
KR20120079065A (en) | 2012-07-11 |
DE102009041250A1 (en) | 2011-05-12 |
JP2013504685A (en) | 2013-02-07 |
CN102471911A (en) | 2012-05-23 |
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